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The sulfur reduction reaction (SRR) plays a central role in high-capacity lithium sulfur (Li-S) batteries. The SRR involves an intricate, 16-electron conversion process featuring multiple lithium polysulfide intermediates and reaction branches1-3. Establishing the complex reaction network is essential for rational tailoring of the SRR for improved Li-S batteries, but represents a daunting challenge4-6. Herein we systematically investigate the electrocatalytic SRR to decipher its network using the nitrogen, sulfur, dual-doped holey graphene framework as a model electrode to understand the role of electrocatalysts in acceleration of conversion kinetics. Combining cyclic voltammetry, in situ Raman spectroscopy and density functional theory calculations, we identify and directly profile the key intermediates (S8, Li2S8, Li2S6, Li2S4 and Li2S) at varying potentials and elucidate their conversion pathways. Li2S4 and Li2S6 were predominantly observed, in which Li2S4 represents the key electrochemical intermediate dictating the overall SRR kinetics. Li2S6, generated (consumed) through a comproportionation (disproportionation) reaction, does not directly participate in electrochemical reactions but significantly contributes to the polysulfide shuttling process. We found that the nitrogen, sulfur dual-doped holey graphene framework catalyst could help accelerate polysulfide conversion kinetics, leading to faster depletion of soluble lithium polysulfides at higher potential and hence mitigating the polysulfide shuttling effect and boosting output potential. These results highlight the electrocatalytic approach as a promising strategy for tackling the fundamental challenges regarding Li-S batteries.

Sodium-ion storage technologies are promising candidates for large-scale grid systems due to the abundance and low cost of sodium. However, compared to well-understood lithium-ion storage mechanisms, sodium-ion storage remains relatively unexplored. Herein, we systematically determine the sodium-ion storage properties of anatase titanium dioxide (TiO2(A)). During the initial sodiation process, a thin surface layer (~3 to 5 nm) of crystalline TiO2(A) becomes amorphous but still undergoes Ti4+/Ti3+ redox reactions. A model explaining the role of the amorphous layer and the dependence of the specific capacity on the size of TiO2(A) nanoparticles is proposed. Amorphous nanoparticles of ~10 nm seem to be optimum in terms of achieving high specific capacity, on the order of 200 mAh g-1, at high charge/discharge rates. Kinetic studies of TiO2(A) nanoparticles indicate that sodium-ion storage is due to a surface-redox mechanism that is not dependent on nanoparticle size in contrast to the lithiation of TiO2(A) which is a diffusion-limited intercalation process. The surface-redox properties of TiO2(A) result in excellent rate capability, cycling stability and low overpotentials. Moreover, tailoring the surface-redox mechanism enables thick electrodes of TiO2(A) to retain high rate properties, and represents a promising direction for high-power sodium-ion storage.

The sluggish electrochemical kinetics of sulfur species has impeded the wide adoption of lithium-sulfur battery, which is one of the most promising candidates for next-generation energy storage system. Here, we present the electronic and geometric structures of all possible sulfur species and construct an electronic energy diagram to unveil their reaction pathways in batteries, as well as the molecular origin of their sluggish kinetics. By decoupling the contradictory requirements of accelerating charging and discharging processes, we select two pseudocapacitive oxides as electron-ion source and drain to enable the efficient transport of electron/Li+ to and from sulfur intermediates respectively. After incorporating dual oxides, the electrochemical kinetics of sulfur cathode is significantly accelerated. This strategy, which couples a fast-electrochemical reaction with a spontaneous chemical reaction to bypass a slow-electrochemical reaction pathway, offers a solution to accelerate an electrochemical reaction, providing new perspectives for the development of high-energy battery systems.

Ceramics are an important class of materials with widespread applications because of their high thermal, mechanical, and chemical stability. Computational predictions based on first principles methods can be a valuable tool in accelerating materials discovery to develop improved ceramics. It is essential to experimentally confirm the material properties of such predictions. However, materials screening rates are limited by the long processing times and the poor compositional control from volatile element loss in conventional ceramic sintering techniques. To overcome these limitations, we developed an ultrafast high-temperature sintering (UHS) process for the fabrication of ceramic materials by radiative heating under an inert atmosphere. We provide several examples of the UHS process to demonstrate its potential utility and applications, including advancements in solid-state electrolytes, multicomponent structures, and high-throughput materials screening.

Thin-film formation and transport properties of two copper-paddlewheel metal-organic framework (MOF) -based systems (MOF-14 and MOF-399) are investigated for their potential integration into electrochemical device architectures. Thin-film analogs of these two systems are fabricated by the sequential, alternating, solution-phase deposition of the inorganic and organic ligand precursors that result in conformal films via van der Merwe-like growth. Atomic force microscopy reveals smooth film morphologies with surface roughnesses determined by the underlying substrates and linear film growth of 1.4 and 2.2 nm per layer for the MOF-14 and MOF-399 systems, respectively. Electrochemical impedance spectroscopy is used to evaluate the electronic transport properties of the thin films, finding that the MOF-14 analog films demonstrate low electronic conductivity, while MOF-399 analog films are electronically insulating. The intrinsic porosities of these ultrathin MOF analog films are confirmed by cyclic voltammetry redox probe characterization using ferrocene. Larger peak currents are observed for MOF-399 analog films compared to MOF-14 analog films, which is consistent with the larger pores of MOF-399. The layer-by-layer deposition of these systems provides a promising route to incorporate MOFs as thin films with nanoscale thickness control and low surface roughness for electrochemical devices.

Charging a commercial lithium-ion battery intercalates lithium into the graphite-based anode, creating various lithium carbide structures. Despite their economic importance, these structures and the dynamics of their charging-discharging transitions are not well-understood. We have videoed single microcrystals of high-quality, natural graphite undergoing multiple lithiation-delithiation cycles. Because the equilibrium lithium-carbide compounds corresponding to full, half, and one-third charge are gold, red, and blue respectively, video observations give direct insight into both the macromolecular structures and the kinematics of charging and discharging. We find that the transport during the first lithiation is slow and orderly, and follows the core-shell or shrinking annuli model with phase boundaries moving at constant velocities (i.e. non-diffusively). Subsequent lithiations are markedly different, showing transport that is both faster and disorderly, which indicates that the initially pristine graphite is irreversibly and considerably altered during the first cycle. In all cases deintercalation is not the time-reverse of intercalation. These findings both illustrate how lithium enters nearly defect-free host material, and highlight the differences between the idealized case and an actual, cycling graphite anode.

Charging a commercial lithium-ion battery intercalates lithium into the graphite-based anode, creating various lithium carbide structures. Despite their economic importance, these structures and the dynamics of their charging-discharging transitions are not well-understood. We have videoed single microcrystals of high-quality, natural graphite undergoing multiple lithiation-delithiation cycles. Because the equilibrium lithium-carbide compounds corresponding to full, half, and one-third charge are gold, red, and blue respectively, video observations give direct insight into both the macromolecular structures and the kinematics of charging and discharging. We find that the transport during the first lithiation is slow and orderly, and follows the core-shell or shrinking annuli model with phase boundaries moving at constant velocities (i.e. non-diffusively). Subsequent lithiations are markedly different, showing transport that is both faster and disorderly, which indicates that the initially pristine graphite is irreversibly and considerably altered during the first cycle. In all cases deintercalation is not the time-reverse of intercalation. These findings both illustrate how lithium enters nearly defect-free host material, and highlight the differences between the idealized case and an actual, cycling graphite anode.

This unit describes a protocol for generation of lung organoids. A lung organoid is a 3D cell/hydrogel composite that resembles the morphology and cellular composition of the human distal lung. These tissue-engineered constructs provide an in vitro model of human lung and are best suited for disease modeling applications. The organoid generation methodology is flexible, allowing for easy scalability in the number of organoids produced and in the ability to accommodate a wide range of cell types. © 2018 by John Wiley & Sons, Inc.

The solution processing of polycrystalline perovskite films introduces trap states that can adversely affect their optoelectronic properties. Motivated by the use of small-molecule surfactants to improve the optoelectronic performance of perovskites, we demonstrate the use of polymers with coordinating groups to improve the performance of solution-processed semiconductor films. The use of these polymer modifiers results in a marked change in the electronic properties of the films, as measured by both carrier dynamics and overall device performance. The devices grown with the polymer poly(4-vinylpyridine) (PVP) show significantly enhanced power conversion efficiency from 16.9 ± 0.7% to 18.8 ± 0.8% (champion efficiency, 20.2%) from a reverse scan and stabilized champion efficiency from 17.5 to 19.1% [under a bias of 0.94 V and AM (air mass) 1.5-G, 1-sun illumination over 30 min] compared to controls without any passivation. Treating the perovskite film with PVP enables a VOC of up to 1.16 V, which is among the best reported for a CH3NH3PbI3 perovskite solar cell and one of the lowest voltage deficits reported for any perovskite to date. In addition, perovskite solar cells treated with PVP show a long shelf lifetime of up to 90 days (retaining 85% of the initial efficiency) and increased by a factor of more than 20 compared to those without any polymer (degrading to 85% after ~4 days). Our work opens up a new class of chemical additives for improving perovskite performance and should pave the way toward improving perovskite solar cells for high efficiency and stability.

The intermittent nature of renewable energies requires highly reliable grid-level energy storage approaches. A critical consideration in developing this technology is the areal capacity which determines battery performance and influences the cost of battery technology. Of related importance is finding new ways of developing scalable electrodes. In recent years, three-dimensional (3D) printing of conductive scaffolds has emerged as an alternative to overcome the scalability limitations of commercial tape cast electrodes. The research carried out in the current study demonstrates a successful scalability pathway for nanoscale VO2(B), a desirable cathode for sodium-ion batteries which has a nano-flower morphology with a crystallite size < 20 nm. By electrodepositing VO2(B) onto a graphene aerogel scaffold, we were able to achieve mass loading of over 100 mg·cm−2 and still possess an areal capacity of 10 mAh·cm−2 at a current density of 5 mA·cm−2. Moreover, after 1000 cycles, these electrodes retained 75% to 80% of their initial capacity. Even at high loading levels, the electrodeposited VO2(B) exhibits pseudocapacitive material signatures such as a box-like voltammetry response, linear galvanostatic response, and no phase change upon lithiation. The scalability of the VO2(B) electrode is demonstrated in a series of experiments which show the areal capacity to scale upon increase in both mass loading and electrode thickness, with only small changes in specific capacity. This study establishes that nanoscale materials can be scaled up to achieve thick electrodes without compromising their electrochemical properties. [ABSTRACT FROM AUTHOR]

Stem cell technologies, especially patient-specific, induced stem cell pluripotency and directed differentiation, hold great promise for changing the landscape of medical therapies. Proper exploitation of these methods may lead to personalized organ transplants, but to regenerate organs, it is necessary to develop methods for assembling differentiated cells into functional, organ-level tissues. The generation of three-dimensional human tissue models also holds potential for medical advances in disease modeling, as full organ functionality may not be necessary to recapitulate disease pathophysiology. This is specifically true of lung diseases where animal models often do not recapitulate human disease. Here, we present a method for the generation of self-assembled human lung tissue and its potential for disease modeling and drug discovery for lung diseases characterized by progressive and irreversible scarring such as idiopathic pulmonary fibrosis (IPF). Tissue formation occurs because of the overlapping processes of cellular adhesion to multiple alveolar sac templates, bioreactor rotation, and cellular contraction. Addition of transforming growth factor-β1 to single cell-type mesenchymal organoids resulted in morphologic scarring typical of that seen in IPF but not in two-dimensional IPF fibroblast cultures. Furthermore, this lung organoid may be modified to contain multiple lung cell types assembled into the correct anatomical location, thereby allowing cell-cell contact and recapitulating the lung microenvironment. Our bottom-up approach for synthesizing patient-specific lung tissue in a scalable system allows for the development of relevant human lung disease models with the potential for high throughput drug screening to identify targeted therapies. Stem Cells Translational Medicine 2017;6:622-633.

Bronchopulmonary dysplasia (BPD) is a leading complication of premature birth and occurs primarily in infants delivered during the saccular stage of lung development. Histopathology shows decreased alveolarization and a pattern of fibroblast proliferation and differentiation to the myofibroblast phenotype. Little is known about the molecular pathways and cellular mechanisms that define BPD pathophysiology and progression. We have developed a novel three-dimensional human model of the fibroblast activation associated with BPD, and using this model we have identified the Notch pathway as a key driver of fibroblast activation and proliferation in response to changes in oxygen. Fetal lung fibroblasts were cultured on sodium alginate beads to generate lung organoids. After exposure to alternating hypoxia and hyperoxia, the organoids developed a phenotypic response characterized by increased α-smooth muscle actin (α-SMA) expression and other genes known to be upregulated in BPD and also demonstrated increased expression of downstream effectors of the Notch pathway. Inhibition of Notch with a γ-secretase inhibitor prevented the development of the pattern of cellular proliferation and α-SMA expression in our model. Analysis of human autopsy tissue from the lungs of infants who expired with BPD demonstrated evidence of Notch activation within fibrotic areas of the alveolar septae, suggesting that Notch may be a key driver of BPD pathophysiology.